problems and perspectives

Marine Chemistry 63 Ž1999. 293–309
Biomarkers as organic-carbon-source and environmental
indicators in the Late Quaternary Arctic Ocean:
problems and perspectives
Kirsten Fahl ) , Ruediger Stein
Alfred-Wegener-Institute for Polar and Marine Research, BremerhaÕen, Germany
Abstract
In order to examine the variation in marine and terrigenous sources of the organic matter during the last 15,000 Cal. yr
BP, hydrogen index values, CrN ratios, and specific biomolecules Žshort- and long-chain n-alkanes, short-chain fatty acids,
sterols, alkenones, and pigments. were determined in three sediment cores from the Laptev Sea continental margin. The
results show that the interpretation of the biomarker data is much more complicated and less definitive in comparison to
similar data sets from low-latitude open-ocean environments. This is mainly caused by the complexity of the Arctic Ocean
system, which is characterized by a high seasonality of sea-ice cover and primary productivity, sea-ice sediment transport
and a high fluvial supply of freshwater Žaquatic. organic matter. A combination of organic geochemical, organic
petrographic and micropaleontological data may yield to a more precise identification of organic-carbon sources for these
complex systems. On the Laptev Sea shelf Žcores KD9502-14 and PS2725-5., terrigenous organic-carbon input controlled by
river discharge seems to be predominant during the last about 10,000 Cal. yr BP. Maximum supply of terrigenous organic
carbon was reached in the Early Holocene Ži.e., about 9000–10,000 Cal. yr BP.. Further offshore at the upper continental
slope Žcore PS2458-4., a major change in organic-composition occurred near 10,000 Cal. yr BP. During this period hydrogen
indices as well as the amounts of short-chain n-alkanes, short-chain fatty acids, dinosterol and brassicasterol significantly
increased, indicating increased relative proportions of marine organic matter preserved in the later time interval. q 1999
Elsevier Science B.V. All rights reserved.
Keywords: marine and terrigenous organic carbon; biomarker; paleoproductivity; Laptev Sea; Arctic Ocean
1. Introduction
The present state of the Arctic Ocean and its
influence on the global climate system strongly depends on river discharge Žsee Stein Ž1998. for re-
)
Corresponding author. Fax: q49-4831-580; E-mail:
kfahl@awi-bremerhaven.de
view.. The freshwater balance of the Arctic Ocean,
which receives 10% of the global runoff ŽAagaard
and Carmack, 1989., plays a key role in controlling
sea-ice extent and intermediaterbottom water formation in the Northern Hemisphere, as well as Arctic
Ocean surface-water conditions. The major Arctic
rivers also supply huge amounts of suspended inorganic Ždetrital. and organic matter to the shelves and
the detrital component of Arctic shelf sediments,
0304-4203r99r$ - see front matter q 1999 Elsevier Science B.V. All rights reserved.
PII: S 0 3 0 4 - 4 2 0 3 Ž 9 8 . 0 0 0 6 8 - 1
294
K. Fahl, R. Stein r Marine Chemistry 63 (1999) 293–309
thus, largely consists of riverine material. The annual
discharge of suspended sediments by the Lena River,
for example, is presently 17.6)10 6 tons ŽMartin et
al., 1993.. Concerning the sources and fate of organic matter within the Arctic system, Arctic rivers
which discharge large quantities of terrigenous organic matter, but also nutrients, into the system, are
of considerable importance. Dissolved and particulate organic matter supplied by the Lena River is
estimated at 3.6)10 6 tonsryr and 1.3)10 6 tonsryr,
respectively ŽRachold et al., 1996.. The riverine
nutrient supply may cause enhanced surface-water
productivity. This is reflected by elevated chlorophyll a concentrations and phytoplankton cell numbers in the Lena River plume ŽHeiskanen and Keck,
1996.. The concentrations of dissolved silica are
high throughout the year within the Lena River
Ž43–108 mM., whereas nitrate and phosphate are
low Ž1.4–16 mM and 0.1–0.8 mM, respectively.
ŽLetolle
et al., 1993; Cauwet and Sidorov, 1996;
´
Gordeev et al., 1996.. Within the Lena River phytoplankton productivity, thus, seems to be limited by
nutrients other than silica ŽHeiskanen and Keck,
1996.. This may suggest that the linkage between
riverine nutrient supply and enhanced productivity is
not necessarily a simple direct relationship.
Most of the organic matter accumulates in coastal
zones; however, significant amounts of this material
are transported further offshore by different processes such as sea-ice, ocean currents, and turbidity
currents ŽStein and Korolev, 1994; and further references therein.. Eolian input is only of very minor
importance for the sedimentary budget of the Arctic
Ocean. Macdonald et al. Ž1998. estimated the eolian
flux in the Mackenzie shelf area, reaching 1.4)10 4
tonsryr. Based on studies of snow samples from the
western central Arctic Ocean an eolian flux of 3.3–
14.0 mgrcm2 and year was calculated ŽDarby et al.,
1974, 1989.. Even if all this material would be
released during summer melting and would reach the
sea floor Žwhich is not very realistic., this would
result in an average sedimentation rate of 0.02–0.09
mmrkyr, i.e., about 1–5% of the bulk sedimentation
rate. In our study area, the Laptev Sea continental
margin where Holocene bulk sedimentation rates
increase to values of about 15 to 800 cmrkyr ŽStein
and Fahl, 1998., the eolian input then becomes even
much less important.
Comparison of sedimentological and organic-geochemical proxies in surface sediments reflecting the
surface water productivity and terrigenous organiccarbon flux with physical and biological parameters
provides a means to identify the most important
processes controlling the organic-carbon accumulation in the Arctic Ocean Že.g., Fahl and Stein, 1997;
Schubert and Stein, 1997; Stein et al., 1998.. Interpretation of vertical profiles in sediment cores in the
context of these findings will then yield information
on changes in the organic-carbon cycle of the Arctic
Ocean through time. These data may, in turn, yield
important insights into the role of the Arctic Ocean
during global climate change.
The use of specific organic-geochemical tracer
compounds Žbiomarkers. as Žpaleo-. environmental
proxies is a well established tool in low- and midlatitude open-ocean areas Že.g., Farrimond et al.,
1990; ten Haven et al., 1990; Prahl et al., 1994;
Hinrichs et al., 1995.. When using biomarkers as
Žpaleo-. indicators of spatial and temporal changes in
organic-carbon sources for high-latitude ice-covered
regions, such as the Laptev Sea continental margin
and adjacent deep sea, it is important to consider the
complex factors controlling the organic-carbon flux
in these areas. First, the strong fluvial supply may
provide freshwater Žaquatic. organic matter as well
as terrestrial organic matter. Second, due to the more
or less closed sea-ice cover, phytoplankton productivity in the Arctic Ocean is very low and represents
a mixed signal of surface-water productivity and
productivity of sea-ice communities. Third, the organic matter deposited on the Laptev Sea shelf,
which is a mixture of terrigenous higher plant material, freshwater organic material and, to a limited
extent, marine organic matter, may be incorporated
into the sea-ice and further transported offshore.
Thus, terrigenous organic matter may be deposited
far away from the source area.
The major goal of this study is Ž1. to discuss the
problems of using biomarkers as organic-carbonsource indicators in Arctic Ocean sediments, Ž2. to
identify organic-carbon sources Ži.e., marine vs.
aquatic vs. terrigenous., and Ž3. to reconstruct
changes in composition and flux of organic carbon in
relation to climate change and sea-level rise at the
Laptev Sea continental margin during the last ;
15,000 Cal. yr BP.
K. Fahl, R. Stein r Marine Chemistry 63 (1999) 293–309
2. Sediments and stratigraphy
The three sediment cores described in this study,
PS2458-4, PS2725-5, and KD9502-14 ŽFig. 1, Table
295
1., were obtained during RV Polarstern Expedition
ARK-IXr4 1993 ŽFutterer,
1994., RV Polarstern
¨
Expedition ARK-XIr1 1995 ŽRachor, 1997., and
TRANSDRIFT-III Expedition 1995 with RV Kapi-
Fig. 1. Location of cores KD9502-14, PS2725-5, and PS2458-4 from the Laptev Sea and the continental margin. Grey arrows indicate the
Transpolar Drift System ŽPfirman et al., 1989..
K. Fahl, R. Stein r Marine Chemistry 63 (1999) 293–309
296
Table 1
Position, water depth and recovery of sediment cores taken during the 1993 and 1995 RV Polarstern and Kapitan Dranitsyn cruises
Core
Gear
KD9502-14
Vibro corer
PS2725-5
Gravity corer
PS2458-4
Kastenlot
Position
Water depth Žm.
Inner Laptev Sea
X
X
76811.52 N
133806.99 E
Western East Siberian Sea
X
X
78839.36 N
144808.1 E
Eastern Laptev Sea
X
X
78809.95 N
133823.86 E
tan Dranitsyn ŽKassens, 1997., respectively. The
sampling was carried out using a Kastenlot, gravity
corer, and vibro corer.
Recovery Žm.
46
2.30
77
4.78
983
8.00
last ; 15,000 Cal. yr BP. At a depth of 100 cmbsf,
there is evidence of a hiatus lasting 6–8000 years;
the upper 100 cm are probably not older than 100–
200 Cal. yr BP ŽSpielhagen et al., 1996..
2.1. Inner LapteÕ Sea shelf
Core KD9502-14 from the Laptev Sea shelf east
of the New Siberian Islands ŽTable 1. consists of
olive gray silty clay ŽKassens, 1997.. Based on
AMS-14 C dating, the sedimentary sequence probably
represents the last ; 8000 Cal. yr BP ŽBauch et al.,
1996..
3. Methods
Core PS2725-5 was obtained from the shelf of the
western East Siberian Sea, north of the New Siberian
Islands ŽTable 1.. The 4.8 m long sedimentary sequence is dominated by very dark gray, dark olive,
and black silty clay with common to abundant black
spotsrlayers between 30 and 178 cmbsf ŽRachor,
1997.. The lowermost 40 cm contain significant
amounts of sand. Based on AMS-14 C dating performed on bivalves, the sediments represent the last
; 10,000 Cal. yr BP ŽStein and Fahl, 1998..
The bulk parameters Žtotal nitrogen and organiccarbon contents. were determined by means of a
Heraeus CHN-analyzer Žfor details concerning the
method see Stein, 1991.. CrN ratios were calculated
as ‘total organic carbonrtotal nitrogen ratios’ based
on weight percentage. The Rock–Eval parameters
hydrogen index ŽHI in mg HCrg TOC. and oxygen
index ŽOI in mg CO 2rg TOC. were determined as
described by Espitalie´ et al. Ž1977..
For the lipid analyses the sediment samples were
stored at y808C or in dichloromethane:methanol
Ž2:1, by vol.. at y238C until further treatment. The
sediment Ž8 g. was homogenised, extracted and purified as recommended by Folch et al. Ž1957. and
Bligh and Dyer Ž1959.. An aliquot of the total
extract was used for analyzing n-alkanes, sterols and
alkenones.
2.3. Eastern LapteÕ Sea
3.1. n-Alkanes
Core PS2458-4 taken from the upper eastern
Laptev Sea continental slope ŽTable 1., consists of a
8 m long sedimentary sequence of very dark olivegray silty clay of dominantly terrigenous origin
ŽFutterer,
1994.. The upper 25 cm are of dark brown
¨
to very dark brown color. Small bivalves occasionally occur, and these bivalves were used for AMS-14 C
dating ŽSpielhagen et al., 1996.. Based on these
dates, the sediments of core PS2458-4 represent the
The alkanes were separated from the other fractions by column chromatography using hexane as
eluent. The composition of this fraction was analysed
with a Hewlett Packard gas chromatograph ŽHP 5890,
column 50 m = 0.25 mm; film thickness 0.25 mm;
liquid phase: HP 1. using a temperature program as
follows: 608C Ž1 min., 1508C Žrate: 108Crmin.,
3008C Žrate: 48Crmin., 3008C Ž45 min isothermal..
The injection volume was 1 ml ŽCold Injection Sys-
2.2. East Siberian Sea
K. Fahl, R. Stein r Marine Chemistry 63 (1999) 293–309
tem: 608C Ž5 s., 3008C Ž60 s., rate: 108Crs.. Helium
was used as carrier gas. The composition was verified by comparison with a standard mixture; for the
quantification squalane was added before any analytical step.
3.2. Alkenones
The alkenones were separated from the other
fractions by column chromatography using hexane:
ethylacetate Ž95:5 and 90:10, by vol.. as eluent. A
saponification step with 1 M potassium hydroxide in
95% methanol for 2 h at 908C followed. The fraction
was analysed by means of a Hewlett Packard gas
chromatograph Žas described for the n-alkane analysis. using a temperature program as follows: 608C Ž1
min., 2708C Žrate: 208Crmin., 3208C Žrate:
18Crmin., 3208C Ž20 min isothermal.. The injection
volume was 1 ml ŽCold Injection System: 608C,
1058C Žrate: 38Crs., 3208C Žrate: 108Crs., 3208C
Ž60 s isothermal.. The identification of the alkenones
was carried out by means of retention time. For
quantification octacosanoic acid methyl ester was
used as an internal standard.
3.3. Fatty acids
An aliquot of the total extract was used for
preparing fatty acid methyl esters and free alcohols
by transesterification with 3% concentrated sulfuric
acid in methanol for 4 h at 808C. After extraction
with hexane, the composition was analysed with a
Hewlett Packard gas chromatograph ŽHP 5890, column 30 m = 0.25 mm; film thickness 0.25 mm;
liquid phase: DB-FFAP. using a temperature program as follows: 1608C, 2408C Žrate: 48Crmin.,
2408C Ž15 min isothermal. Žmodified according to
Kattner and Fricke, 1986.. The injection volume is 1
ml. The fatty acids and alcohols were identified by a
standard mixture ŽMarinol standard was kindly made
available by J.R. Sargent, Scotland.. For quantification, an internal standard Ž19:0 fatty acid methyl
ester. was added.
297
amide. Ž608C for 2 h.. After extraction with hexane,
the composition was analysed by GCrMS, which
consists of a gas chromatograph ŽHP 5890, column
30 m = 0.25 mm; film thickness 0.25 mm; liquid
phase: HP 5. and a mass spectrometer ŽMSD, HP
5972, 70 eV electron-impact-ionisation, Scan 50–650
mrz, 1 scanrs, ion source temperature 1758C.. GC
analysis was performed with the following temperature program: 608C Ž1.55 min., 2008C Žrate:
208Crmin., 3008C Žrate: 58Crmin.. The injection
volume is 1 ml Žsplitless.. Helium was used as
carrier gas Ž1.2 mlrmin at 608C.. The identification
of the sterols was carried out on basis of GC retention time and MS fragmentation pattern. For quantification, cholest-5-en-3b-ol-2,2,3,4,4,6-d 6 Žinternal
standard. was added before any analytical step. Note
that only the 4a-23,24-trimethyl-5a-cholest-22 E-en3b-ol Ždinosterol. and 24-methylcholesta-5,22 Edien-3b-ol Žbrassicasterol. were used for interpretation.
3.5. Pigments
The tetrapyrrolic pigments have been determined
by measuring the absorbance of their solvent extract
Ž90% acetone. at a wavelength of 410 nm ŽRosellMele,
´ 1994; Rosell-Mele´ and Koc, 1997.. Additionally, the measurement was carried out at 645 and 663
nm to determine chlorophyll abundances. The turbidity factor Žabsorbance at 750 nm. has been subtracted.
3.6. Carbon-reference-index (CPI)
The relation of odd-to-even chain length of the
n-alkanes as an estimate for the thermal maturity
of the terrigenous organic matter was calculated
as CPI s ŽC 21 q C 23 q C 25 q C 27 q C 29 q C 31 .r
ŽC 22 q C 24 q C 26 q C 28 q C 30 q C 32 . Žafter Bray
and Evans, 1961..
4. Biomarkers as organic-carbon source and environmental indicators
3.4. Sterols
An aliquot of the total extract was silylated with
100 ml BSTFA Žbis-trimethylsilyl-trifluoroacet-
Several biomolecules are frequently used as
biomarkers indicative for the origin of organic matter
in sediments in order to derive information about the
298
K. Fahl, R. Stein r Marine Chemistry 63 (1999) 293–309
Žpaleo-. environmental conditions. The distribution
and significance of these molecular fossils are quite
well established in temperate low and mid-latitude
regions and oceanic areas subject to minor fluvial
influence Že.g., Farrimond et al., 1990; ten Haven et
al., 1990; Prahl et al., 1994; Hinrichs et al., 1995..
When using biomarkers in the Laptev Sea and the
adjacent Arctic Ocean, the different transport processes, which are dominated by river discharge, seaice transport, downslope transport, and vertical and
lateral transport through the water column, have to
be considered. The unambiguous importance of the
Siberian rivers is reflected by the high input of
terrigenous Žhigher-plant and aquatic. organic matter
onto the shelf and into the adjacent slope and deep
sea area. Accordingly, up to 98% of the TOC represents terrigenous organic carbon on the Laptev Sea
shelf ŽBoetius et al., 1996., with this proportion
decreasing offshore where marine productivity—
especially at the ice margin—becomes more important ŽFahl and Stein, 1997.. The interpretation of the
biomarker signals are thus much more complex than
in low-latitude regions characterized by minor fluvial
input and the lack of sea-ice influence. In these latter
areas the complex mixing of lipids from diverse
sources typical for our study area, can be largely
excluded.
In the Laptev Sea continental margin and similar
environments biomarkers such as short-chain n-alkanes, alkenones, short-chain fatty acids, sterols, and
pigments may derive from aquatic Žfreshwater. algae
as well as from marine phyto- and zooplankton Žsee
Table 2.. Consequently a pronounced algal signature
is not necessarily marine in origin, and all data have
to be interpreted cautiously. Whereas the long-chain
fatty acids are almost exclusively of terrigenous origin, derived from specific terrestrial higher plants
ŽEglinton and Hamilton, 1963; Madureira et al.,
1995., the short-chain Žsaturated and monorpolyunsaturated. compounds are commonly related to a
marine source Že.g., Kates and Volcani, 1966; Ackman et al., 1968; Harrington et al., 1970; Pohl and
Zurheide, 1979; Falk-Petersen et al., 1987; Fraser et
al., 1989; Volkman, 1989; Fahl and Kattner, 1993..
Specific fatty acid compositions have been described
for marine diatoms, different ice algae ŽKates and
Volcani, 1966; Fahl and Kattner, 1993., marine
Dinophyceae ŽMayzand et al., 1976; Fraser et al.,
1989; Ahlgren et al., 1992., as well as Haptophyceae
ŽSargent et al., 1985, Conte et al., 1994.. Shortchain fatty acids, however, are also found in lacustrinerfreshwater environments ŽAhlgren et al., 1992;
Leveille
´
´ et al., 1997.. As a result, short-chain fatty
acids cannot be used to distinguish between aquatic
and marine inputs ŽTable 2.. The same is true for
pigments ŽTable 2., short-chain n-alkanes Že.g.,
Eglinton and Hamilton, 1963; Venkatesan et al.,
1987; Madureira et al., 1995. and the investigated
sterols. 4 a-23,24-Trimethylcholest-22 E-en-3b-ol
Ždinosterol. is well known as a biosynthetic product
of dinoflagellates ŽBoon et al., 1979; de Leeuw et al.,
1983. and other marine sources ŽNichols et al., 1990;
Volkman et al., 1993., but also occurs in lacustrine
organisms ŽTable 2. and aquatic environments
ŽYunker et al., 1995.. Robinson et al. Ž1984. and
Thiel Ž1993., for example, determined high concentrations of dinosterol in the water column as well as
in the sediments of Lake Van ŽTurkey. and Lake
Table 2
List of different biomarkers from marine and freshwater origin
Compounds
Marine
Freshwaterrnon-marine
Short-chain n-alkanes ŽC 15 q C 17 q C 19 .
Long-chain n-alkanes ŽC 27 q C 29 q C 31 .
Short-chain fatty acids ŽC 12 to C 24 .
Hinrichs et al., 1995
McKirdy et al., 1986
Yunker et al., 1995
Kates and Volcani, 1966
Ahlgren et al., 1992
Tayler, 1987
Thiel, 1993
Tayler, 1987
Thiel, 1993
Yunker et al., 1995
Thiel et al., 1997
Stryer, 1987
4a-23,23-Trimethyl-5a-cholest-22 E-en-3b-ol
ŽDinosterol.
24-Methylcholesta-5,22 E-dien-3b-ol
ŽBrassicasterol.
Long-chain alkenones ŽC 37:4 q C 37:3 q C 37:2 .
Chlorophyll a, b, c
Fahl and Kattner, 1993
Nichols et al., 1984
Nichols et al., 1984
Nichols et al., 1984
Conte et al., 1994
Stryer, 1987
K. Fahl, R. Stein r Marine Chemistry 63 (1999) 293–309
Priest Pot ŽEngland.. High contents of 24-methylcholesta-5,22 E-dien-3b-ol Žbrassicasterol. were also
measured in this lacustrinerfreshwater environment
ŽThiel et al., 1997; Table 2., reflecting the presence
of diatoms, dinoflagellates or haptophytes ŽConte et
al., 1994.. For the long-chain n-alkanes a terrigenous
origin from higher plants is generally accepted
ŽSalasoo, 1987; Villanueva et al., 1997.. The synthesis of long-chain n-alkanes by some special sulfatereducing bacteria seems to be of minor importance
for the marine environments ŽDavis, 1968.. The
lithology of the investigated cores displays a change
from dark brown Žoxic. to dark olive colours between 20 and 30 cmbsf indicating a reducing milieu
in the lower core section. Thus, the influence of
sulfate-reducing bacteria cannot be excluded. Even
the long-chain unsaturated alkenones, usually regarded as a prominent marine coccolithophorid indicator Že.g., Volkman et al., 1980; Brassell et al.,
1986; Prahl et al., 1989; Farrimond et al., 1990;
Sikes et al., 1991; Jasper and Gagosian, 1993., were
also detected in lacustrine sediments Že.g., Thiel et
al., 1997.. In our study area, however, the alkenones
are present only in low abundances ŽFahl and Stein,
1997; Stein et al., 1998..
In the Mackenzie river estuary ŽCanadian Arctic.
the biomarker distribution also indicates a significant
aquatic contribution ŽYunker et al., 1995. as suggested for the Lena River.
Based on the arguments outlined above it appears
to be clear that the exclusive use of biomarkers to
distinguish between marine and terrigenousraquatic
sources is questionable, especially in the Laptev Sea
and the adjacent continental slope. In order to solve
this problem and to allow more precise statements
about the organic-carbon origin and its Žpaleo-. environmental significance, it is necessary to combine
the organic-geochemical results with micropaleontological and sedimentological data. In addition, future
work on stable carbon isotopic composition of
biomarkers could yield more information about the
origins of organic carbon and its deposition.
5. Biomarker records in the Laptev Sea continental margin area
In order to understand the sedimentary processes
controlling organic-carbon deposition, as well as the
299
Žpaleo-. environmental changes in the Laptev Sea
and the adjacent continental margin through time, the
three sediment cores, KD9502-14, PS2725-5 and
PS2458-4, were investigated for the distribution of
bulk parameters ŽTOC, HI values, and CrN ratios.
and biomarkers Žlongrshort-chain n-alkanes, shortchain fatty acids, dinosterol, brassicasterol, and pigments..
The depth profiles of the two shelf cores
KD9502-14 and PS2725-5, which span the last ;
8000–1000 Cal. yr BP, show TOC contents between
1 and 1.6% ŽFigs. 2 and 3.. HI values of - 100 mg
HCrg TOC occur throughout the entire records. In a
HI vs. OI Ž‘ van-Krevelen-type’. diagram, all data
points plot into the ‘Krevelen-type III’ field ŽFig. 4A
and B ., reflecting the high proportion of
immaturerfresh terrigenous organic carbon. The
biomarker composition supports the predominantly
terrigenous character of the organic carbon in both
cores ŽFigs. 2 and 3.. In general, the concentrations
of long-chain n-alkanes ŽC 27 q C 29 q C 31 . are high
Ž300–400 mgrg TOC., comprising more than 50%
of the total n-alkanes. The concentrations of the
corresponding short-chain n-alkanes Ž10 mgrg TOC.
and pigments are rather low on the shelf as expected.
In general, the n-alkane composition showing a terrigenous predominance is similar to the ice-free New
England continental margin ŽVenkatesan et al., 1987.,
the Gulf of Mexico ŽJasper and Gagosian, 1993., and
the coastal zone off Washington State influenced by
Columbia River supply ŽPrahl and Muehlhausen,
1989., as well as for the permanent ice-covered
Arctic Ocean ŽSchubert and Stein, 1996.. In all these
environments the ratio of long- to short-chain n-alkanes ranges between 25 and 40. The CPI is high,
varying between 1.8 and 4.3, which also supports the
predominance of fresh terrigenous material in the
cores Žcf. Bray and Evans, 1961.. According to
Brassell et al. Ž1978. and Hollerbach Ž1985., fresh
terrigenous organic matter shows a CPI of 3 to 10,
whereas fossil material varies around 1 depending on
the state of decomposition and thermal alteration.
In contrast to the short-chain n-alkanes, the contents of the short-chain fatty acids 16:0, 16:1Ž n-7.,
16:1Ž n-5., 18:0, 18:1Ž n-9., and 18:1Ž n-7. are surprisingly high Ž300 mgrg TOC; Figs. 2 and 3, Table 3..
These values are similar to those from the Santa
Barbara Basin and the New England continental
300
K. Fahl, R. Stein r Marine Chemistry 63 (1999) 293–309
Fig. 2. Organic-geochemical bulk parameters and specific biomarkers in the sedimentary sequence of core KD9502-14: total organic-carbon contents Ž%., total organic
carbonrtotal nitrogen ŽCrN. ratios, hydrogen index values Žmg HCrg TOC., long- and short-chain n-alkanes Žmgrg TOC., short-chain fatty acids Žmgrg TOC., brassicasterol
Žmgrg TOC., dinosterol Žmgrg TOC., and pigment absorbance values. AMS-14 C ages according to Bauch et al. Ž1996..
K. Fahl, R. Stein r Marine Chemistry 63 (1999) 293–309
Fig. 3. Organic-geochemical bulk parameters and specific biomarkers in the sedimentary sequence of core PS2725-5: total organic-carbon contents Ž%., total organic
carbonrtotal nitrogen ŽCrN. ratios, hydrogen index values Žmg HCrg TOC., long- and short-chain n-alkanes Žmgrg TOC., short-chain fatty acids Žmgrg TOC., brassicasterol
Žmgrg TOC., dinosterol Žmgrg TOC., and pigment absorbance values. AMS-14 C ages according to Stein and Fahl Ž1998..
301
302
K. Fahl, R. Stein r Marine Chemistry 63 (1999) 293–309
Fig. 4. Hydrogen index vs. oxygen index Ž‘ van-Krevelen-type’. diagram of cores KD9502-14 ŽA., PS2725-5 ŽB. and PS2458-4 ŽC.. Roman
numbers mark different kerogen types: I and II marine, III terrigenous organic matter Žclassification after Espitalie´ et al., 1977; Peters,
1986..
margin ŽTable 3., where they have been interpreted
as a marine organic-carbon source indicators. The
same interpretation was published by ten Haven et
al. Ž1990. for the upwelling area off Peru, but there
the concentrations of the short-chain fatty acids are
10 times higher than in the Laptev Sea ŽTable 3., as
expected for high-productivity environments characterized by high marine organic-carbon flux. Ze-
K. Fahl, R. Stein r Marine Chemistry 63 (1999) 293–309
Table 3
Concentrations of biomarkers in sediments from different environments
Area
Type of environment
Lake Van, Turkey
ŽThiel, 1993.
Long-chain n-alkanes
Dinosterol
Brassicasterol
Freshwater environment
Žwater depth: 451 m.
Columbia River
ŽPrahl and Muehlhausen, 1989.
Long-chain n-alkanes
Gulf of Mexico
ŽJasper and Gagosian, 1993.
Long-chain n-alkanes Žodd.
Peru Upwelling Area
ŽFarrimond et al., 1990; ten Haven et al., 1990.
Long-chain n-alkanes
Short-chain n-alkanes
Short-chain fatty acids
Dinosterol
Brassicasterol
Santa Barbara Basin
ŽHinrichs et al., 1995; Stein and Rack, 1995.
Long-chain n-alkanes
Short-chain n-alkanes
Short-chain fatty acids
Dinosterol
Brassicasterol
Cont. margin, New England
ŽVenkatesan et al., 1987.
Long-chain n-alkanes
Short-chain n-alkanes
Fatty acids ŽC12–C32.
Dinosterol
North Atlantic, Biscay Abyssal Plain
ŽMadureira et al., 1995.
Long-chain n-alkanes
Total sterols
Arctic Ocean
ŽSchubert and Stein, 1996.
Long-chain n-alkanes
Short-chain n-alkanes
Laptev Sea shelf
ŽThis paper, average values.
Long-chain n-alkanes
Short-chain n-alkanes
Short-chain fatty acids
Dinosterol
Brassicasterol
362 mgrg TOC
128 mgrg TOC
380 mgrg TOC
High fluvial supply
277 " 87 mgrg TOC
164 mgrg TOC
51 mgrg TOC)
8 mgrg TOC)
5000 mgrg TOC
34 mgrg TOC)
235 mgrg TOC)
91 mgrg TOC
31 mgrg TOC
140–250 mgrg TOC
42 mgrg TOC
40 mgrg TOC
High fluvial supply, hemipelagic
environment
Žwater depth: 2260 m.
High productivity
upwelling environment
Žwater depth: 461 m.
Semi-closed basin with high surfacewater productivity and suboxic bottom
water
Žwater depth: 577 m.
Continental margin, ice-free
Žwater depth: 1280 m.
60.6 mgrg TOC
2.4 mgrg TOC
454 mgrg
136 mgrg TOC
Open ocean, ice-free
Žwater depth: 4105 m.
75 mgrg TOC
150 mgrg TOC
400–700 mgrg TOC
10–20 mgrg TOC
355 mgrg TOC
9 mgrg TOC
300 mgrg TOC
4 mgrg TOC
7 mgrg TOC
Open ocean, permanent sea-ice
cover
Žwater depth: 1500–4000 m.
Shelf, seasonal sea-ice cover,
high fluvial supply
Žwater depth: 46 m.
303
304
K. Fahl, R. Stein r Marine Chemistry 63 (1999) 293–309
Table 3 Žcontinued.
Area
Type of environment
Laptev Sea continental slope
ŽThis paper, average values.
799–360 cmbsf
Long-chain n-alkanes
Short-chain n-alkanes
Short-chain fatty acids
Dinosterol
Brassicasterol
360–0 cmbsf
Long-chain n-alkanes
Short-chain n-alkanes
Short-chain fatty acids
Dinosterol
Brassicasterol
Continental slope, seasonal sea-ice
cover, high fluvial supply
Žwater depth: 948 m.
196 mgrg TOC
7 mgrg TOC
17 mgrg TOC
9 mgrg TOC
22 mgrg TOC
150 mgrg TOC
86 mgrg TOC
50 mgrg TOC
45 mgrg TOC
100 mgrg TOC
)Calculated with 3.5% TOC content ŽSuess et al., 1988..
Values are normalized to TOC content.
gouagh et al. Ž1996. assumed that the high amounts
of short-chain fatty acids they measured in surface
sediments from the Lena Delta and further offshore
in the Laptev Sea ŽSPASIBA 2 Expedition, 1991. are
marine in origin. However, based on the above arguments and the positive correlation with the high
concentration of long-chain n-alkanes, as well as
low hydrogen index values, we infer that the high
concentration of short-chain fatty acids in our records
probably derives from freshwaterraquatic algae Žcf.
Ahlgren et al., 1992; Leveille
´
´ et al., 1997..
The relative abundances of 4a-23,24-trimethyl5a-cholest-22 E-en-3b-ol Ždinosterol. and 24-methylcholesta-5,22 E-dien-3b-ol Žbrassicasterol. reach
concentrations of 6 mgrg TOC in both cores. These
compounds are often used as indicators of marine
inputs Že.g., Nichols et al., 1984., but here their
presence also seems to be due to freshwater algae
ŽTayler, 1987; Thiel, 1993.. First results of micropaleontological investigations and maceral analysis
support this assumption. Low but significant amounts
of freshwater algae occur throughout both shelf cores
without high variabilities ŽMatthiessen, personal
communication, 1997.. In comparison with other
oceanic regimes ŽTable 3., the concentrations of
dinosterol and brassicasterol are rather low. Thus, in
general, the organic-geochemical data of both cores
indicate that the organic carbon which accumulates
on the Laptev Sea shelf is mainly of terrigenousr
aquatic origin, most probably controlled by fluvial
ŽLena. discharge.
In the continental slope core PS2458-4 representing the last ; 15,000 Cal. yr BP ŽSpielhagen et al.,
1996., the sedimentary regime seems to be different.
Although the TOC values are in the same range as
those determined in the shelf cores Ž1–1.5%; Fig. 5.,
the composition of the organic carbon is much more
variable, as indicated by the HI values, CrN ratios
and the biomarker distributions. In the lower core
section Ž790 to 360 cmbsf. low HI values and rather
high concentrations of long-chain n-alkanes ŽC 27 q
C 29 q C 31 . ŽFig. 5. indicate terrigenous organic matter. In general, also the high CPI indices of 2 to 3.5
and a position in the ‘Krevelen-type III’ field of HI
vs. OI diagram ŽFig. 4C. support the high content of
fresh terrigenous organic material. The upper core
section Ž360 to 0 cmbsf., on the other hand, is
characterized by relatively high HI values Žup to 200
mg HCrg TOC. suggesting a more marine character
of the organic material. In the HI vs. OI diagram,
these data points plot above the ‘Krevelen-type III’
line Ži.e., a mixture of marinerterrigenous organic
matter with, however, still a dominance of terrigenous organic material.. The more marine character is
also supported by higher concentrations of shortchain fatty acids, dinosterol, and brassicasterol, which
are mainly derived from diatom andror dinoflagellates Že.g., Kates and Volcani, 1966; Boon et al.,
K. Fahl, R. Stein r Marine Chemistry 63 (1999) 293–309
Fig. 5. Organic-geochemical bulk parameters and specific biomarkers in the sedimentary sequence of core PS2458-4: total organic-carbon contents Ž%., total organic
carbonrtotal nitrogen ŽCrN. ratios, hydrogen index values Žmg HCrg TOC., long- and short-chain n-alkanes Žmgrg TOC., short-chain fatty acids Žmgrg TOC., brassicasterol
Žmgrg TOC., dinosterol Žmgrg TOC., and pigment absorbance values. AMS-14 C age according to Spielhagen et al. Ž1996..
305
306
K. Fahl, R. Stein r Marine Chemistry 63 (1999) 293–309
1979; de Leeuw et al., 1983; Nichols et al., 1990;
Fahl and Kattner, 1993; Volkman et al., 1993.. The
correlation coefficient Ž r 2 . of 0.624 Žfor short-chain
fatty acids. and 0.495 Žfor dinosterols. indicates a
well supported correlation between the hydrogen index and these two biomarkers ŽFig. 6A and B.. The
ratio of long- to short-chain n-alkanes, which reaches
values of 2 to 6, is comparable to the calculated
ratios from high-productivity upwelling areas, including the Santa Barbara Basin ŽTable 3.. A high
proportion of marine organic carbon is confirmed by
micropaleontological and maceral data. Marine par-
ticulate organic matter Žlamalginites and dinoflagellate cysts. occur in significant amounts in this interval of core PS2458-4 ŽBoucsein, personal communication, 1997.. This relative increase in the proportion
of marine organic matter at the Laptev Sea continental slope occurred near 10,000 Cal. yr BP ŽFig. 5.,
i.e., near the end of the last major post-glacial sealevel rise Žcf. Fairbanks, 1989. when the Laptev Sea
shelf became widely flooded. Since that time, the
modern environmental situation appears to have been
established.
Large volumes of sediments and associated organic matter, supplied by the major rivers such as the
Lena, have accumulated on the Laptev Sea shelf.
Modern ŽHolocene. accumulation rates of terrigenous organic matter reach high values of 0.2–2 g C
cmy2 kyry1 at the location of core PS2725-5 ŽStein
and Fahl, 1998.. During a short interval in the Early
Holocene Ži.e., near 9000–10,000 Cal. yr BP. when
the Laptev Sea shelf became flooded and coastal
erosion andror river discharge distinctly increased,
these values may have even reached 10–15 g C
cmy2 kyry1 ŽStein and Fahl, 1998.. Significant proportions of terrigenous organic matter, however, are
also incorporated into the sea-ice and further transported offshore within the Transpolar Drift System
Žcf. Fig. 1.. During melting processes, the organic
Žas well as inorganic. matter becomes released and
settles to the deep-sea floor. Thus, in areas of the
central Arctic Ocean characterized by very low phytoplankton productivity due to the more or less closed
sea-ice cover ŽSubba Rao and Platt, 1984., the majority organic matter in the surface sediments may be
of terrigenous origin ŽStein et al., 1994; Schubert and
Stein, 1996; Stein and Schubert, 1996.. The n-alkane
concentration in the central Arctic Ocean surface
sediments, for example, are very similar to those
determined in the Laptev Sea shelf sediments ŽTable
3..
6. Conclusion
Fig. 6. Hydrogen index Žmg HCrg TOC. vs. short-chain fatty
acids Žmgrg TOC. and hydrogen index Žmg HCrg TOC. vs.
dinosterol Žmgrg TOC. diagrams of core PS2458-4.
) Total organic carbon, hydrogen index, CrN
and biomarker records from the Laptev Sea continental margin provide information about variation in the
input of terrigenous and marine organic carbon during the last 10,000–15,000 Cal. yr BP.
K. Fahl, R. Stein r Marine Chemistry 63 (1999) 293–309
) On the Laptev Sea shelf, Žfluvial. terrigenous
organic matter supply was most important throughout the last about 10,000 Cal. yr BP, with maximum
values reached in the Early Holocene Ži.e., 9000–
10,000 Cal. yr BP..
) On the upper continental slope a major increase
in marine organic matter occurred near 10,000 Cal.
yr BP, when the Laptev Sea shelf became largely
flooded and the modern environmental situation established.
) The comparison of the river-dominated shelf
cores ŽKD9502-14 and PS2725-5. with the continental slope core ŽPS2458-4., where marine productivity
is enhanced, provides an excellent example of the
possible problems and limitations in using biomarkers as terrigenous and marine organic-carbon-source
indicators.
Acknowledgements
We especially thank M. Siebold for technical
assistance. We thank T.I. Eglinton, J. Jasper, M.
Yunker and one anonymous reviewer for numerous
constructive suggestions and comments. This study
was performed within the bilateral Russian–German
multidisciplinary research project ‘System Laptev
Sea’. For discussion of the stratigraphic framework
and further paleoenvironmental data obtained from
Laptev Sea sediments, we would like to thank all
colleagues from AWI and GEOMAR Kiel involved
in this Laptev Sea-Project. The financial support by
the Ministry for Education, Science, Research, and
Technology ŽBMBF. is gratefully acknowledged.
This is contribution No. 1444 of the AlfredWegener-Institute for Polar and Marine Research.
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